Halogenated methylol phenols

ABSTRACT

DIMETHYLOL ALKYL PHENOLS AND LOW POLYMERS THEREOF HAVING AN AVERAGE OF 60 TO 85% OF THE AVAILABLE METHYLOL GROUPS REPLACED BY HALOMETHYL ARE PREPARED. THEY ARE USEFUL IN VULCANIZING VARIOUS ELASTOMERS AT ROOM (AMBIENT) TEMPERATURES. PREFERABLY THE HALOGEN IS BROMINE. ALSO PREFERABLY A ZINC COMPOUND, MOST PREFERABLY ZINC OXIDE, IS PRESENT TO SPEED UP THE VULCANIZATION. THE VULCANIZATION OF LIQUID RUBBERS IS PARTICULARLY EFFECTIVE.

unitgd States Patent 7 ABSTRACT OF THE DISCLOSURE Dimethylol alkylphenols and low polymers thereof having an average of 60 to' 85 of theavailable methylol groups replaced by halomethyl are prepared. They areuseful in vulcanizing various elastomers at room (ambient) temperatures.Preferably the halogen is bromine. Also preferably a zinc compound, mostpreferably zinc oxide, is present to speed up the vulcanization. Thevulcanization of liquid rubbers is particularly effective.

Thepresent invention relates tonovel halomethylated alkyl phenols andtheiruse as curing or vulcanizing agents for elastomers, and especiallyfor liquid elastomers.

The preparation of dimethylol alkyl phenols having a portion of themethylol groups replaced by halomethyl is disclosed in Braidwood Patent2,972,600 and Fusco Patents 3,093,613 and 3,165,496. Thesehalomethylated phenols are disclosed as being useful in the conventionalhot vulcanization of solid butyl rubber. Braidwood has relatively lowamounts of halogen, e.g. to 9% bromine, Fusco can have more halogen,e.g. 0.3 to 4 moles per mole of polymethylol phenol. However, Fuscopoints out that his polymethylol phenols can be polymeric and hence themolar amount of halogen per phenol unit is considerably less. Fuscorefers to the halogen being '1 to 60 weight percent of the halogenatedpolymethylol hydrocarbon substituted phenol and that the amount ofhalogen varies with the particular halogen. Thus with iodine theheaviest halogen the weight percent-of halogen is highest. Fusco pointsout thatwith chlorine or bromine the preferred weight percent is 2 to16% and with iodine to 30%. The preferred bromine content is 3 to 7%with a dimethylol 'p-octylphenol resin.

It has now been found that valuable products are obtained if dimethylolp-alkyl phenols and low polymers thereof (i.e. compounds generallyhaving 1 to 6 phenolic nuclei and averaging 1 to 4 phenolic nuclei) arehalogenated so as to replace an average of 60 to 85% of the availablemethylol groups with halomethyl groups. The preferred halogen isbromine. Less preferably iodine can be used as the halogen of thehalomethyl group. Preferably about 65-75% of the available methylolgroups are replaced by bromomethyl (or iodomethyl). The-product obtainedis a liquid mixture of monomer and oligomer. This mixture has 60-85% ofthe theoretical halogen assuming the entire mixture was monomer, howeversince the product has a considerableamountof oligomer in it, the halogencan be actually veryclose to. the theoretical for the total availablemethylol groups, i.e. the hydroxyls of the available methylol groupshave been substantially ,completely replaced by halogen. It is criticalthat the mixture beliquid for satisfactory mixing with liquid elastomersto get uniform dispersion and cure. Crystalline mater-ials such asdihalomethyl alkyl phenols are-not satisfactory.

,j The materials which are halogenated are 2,6-dihydroxymethyl4-alkyl(or 4-aryl) phenols and resitols thereof having up .to 6 phenolicnuclei, usually averaging not over 4 phenolic nuclei. The alkyl groupcan have no 20 carbon atoms but preferably .has at least 4 carbon atoms.Thus ambient temperatures.

3,752,780 Patented Aug. 14, v1973 ICC there can be used the dimethylol4-alkyl phenols and corresponding resitols shown in the aforementionedBraidwood and Fusco patents, 2,6-dimethylol p-cresol, 2,6-dimethylolp-isopropyl phenol, 2,6-dimethylol 4-butylphenol, 2,6-(1i? methylol 4t-butylphenol, 2,6-dimethylol-4-octylphenol, 2,6 dimethylol 4-tt-octylphenol, 2,6-dimethylol 4-p-tamylphenol, 2,6-dimethylol 4-p dodecylphenol, 2,6-dimethylol 4-p-eicosyl phenol, 2,6-dimethylol4-p-tetradecylphenol, 2,6-dimethylol 4-p-hexyl phenol, 2,6-dimethylol- 4(3' methyDpentyl phenol (also called 2,6-dimethylol 4-p-t-hexylphenol),2,6-dimethylol 4-p-nonyl phenol (the nonylphenol being formed byalkylation of mixed nonenes with phenol), 2,6-dimethylol 4-p-cyclohexylphenol, 2,6- dimethylol 4 p-phenyl phenol, 2,6-dimethylol4'-cumylphenol. 2,6-dimethylol 4-hexadecyl phenol. The correspondingresitols having up to 6 phenol units are also in cluded. In fact in mostprocedures for making the 2,6-dimethylol p-alkyl phenols they areprepared admixed with low molecular weight polymers, i.e. resitols,

The halomethyl phenols of the present invention unexpectedly have beenfound to be useful as ambient, i.e. room temperature curing orvulcanizing agents for many elastomers, and especially for many liquidelastomers. The term room temperature curing agents means that thecuring can be initiated Without the application of external heat. Thereaction is exothermic and during the curing the temperature may rise to80 C. or even 100 C. The exotherm can be controlled with externalcooling if desired. i

The halomethylated compounds of the invention, e.g. the brominateddimethylol p-octylphenol having about 75% of the methylol groupsreplaced by bromomethyl and having 27-32% (usually 28-31%) of bromine inthe molecule and having an average molecular weight of 500 andidentified hereinafter as CRJ-328, cross link liquid. elastomers such asliquid hydroxy terminated butadienestyrene copolymer, liquid hydroxyterminated butadieneacrylonitrile copolymer, liquid hydroxy terminatedpolybutadiene, liquid sodium polymerized polybutadiene, liquid lithiumpolymerized polybutadiene, liquid isobutylene-isoprene copolymer, liquidcarboxy terminated butadiene (does not 'cure as well as some of theother polymers), liquid mercaptan terminated butadiene-acrylonitrilecopolymer, liquid isoprene polymers, e.g. partially depolymerizedrubber, all can be vulcanized at Solid butyl rubber likewise can becured at ambient temperature. The use of liquid elastomers is preferredbecause of the scorchy nature of the halomethyl phenolic resincuratives.

The vulcanizing reaction of the bromomethylated phenols of the presentinvention is catalyzed by the addition of zinc compounds such as zincoxide, zinc resinate, zinc naphthenate, and zinc salicylate. Zinc oxideis preferred. The exact amount of zinc compound is not critical but willvary to some extent with the elastomer to be vulcanized. Thus as littleas 1% of zinc oxide based on the elastomer is effective. Likewise theamount of bromomethylated phenol curing agent is not critical and willvary with the particular elastomer, rate of. cure vdesired, etc.

The bromomethylated compounds and the iodomethylated compounds of thepresent invention provide the first phenolic system to enable ambienttemperature vulcanization of elastomers of both the functionalcontaining variety and elastomers containing uns'aturation as the solereactive sites. The vulcanization is believed to proceed through theunsaturated or at the allylic hydro gen. In the elastomers which containactive hydrogensuch as hydroxy terminated butadiene possibly thereaction also takes place at the hydroxy] group, e.g. by splittingolfHBr.

To obtain stability in the formation of the bromomethylated products itis frequently desirable to add a chelating agent, particularly ironchelating agents such as Versene Iron specific (mono sodium salt ofN,N'-dihydroxyethyl glycine).

The amount of bromine in the bromomethylated phenols of the invention ispreferably in the range of the highest amount that the particularmethylolated alkyl phenol can react with and be stable to storage, i.e.the product should not be a corrosive mixture which spontaneouslyself-eliminates 'HBr. C-RJ-328 illustrates a preferred form ofbromomethylated product which is stable to storage and which isactivated by being mixed with zinc compounds.

As stated in the vulcanization it is especially preferred to employ zincoxide in the vulcanization due to its ability to scrub the HBr or HIbyproduct of the vulcanization.

The presence of strongly alkaline materials should be avoided in thevulcanization since significant amounts of such alkaline materials, e.g.alkali metal hydroxides and alkaline earth hydroxides or alkaline amineskill" the room temperature vulcanization. Anything which will competewith the elastomer for the bromomethyl groups or interfere with thedesired vulcanization reaction of course should be avoided in thereaction.

As used in the following examples CRI-328 was diluted with 5 to 7% oftoluene to give a viscosity of approximately 15000 centipoise forhandling purposes. The presence of toluene in the composition is notessential.

It should be realized that some elastomers will not vulcanize with thecompounds of the invention, e.g. Hycar 1312 a liquidbutadiene-acrylonitrile elastomer does not normally vulcanize.

The starting dimethylol p-alkyl (or aryl) phenols and resitols areprepared in conventional fashion by reacting approximately 2 moles offormaldehyde with 1 mole of a para alkyl phenol using alkalinecatalysis, for example NaOH, KOH or MgO as shown for example in theBraidwood and Fusco patents. The dimethylol para alkyl (or aryl) phenolsand resitols are then separated from the alkaline catalyst byneutralization and washing. The methylolated alkyl phenolic product isthen reacted with aqueous hydrobromic acid to form the bromomethylgroups with some residual hydroxymethyl groups still remaining to give aproduct having the formula XHzC CHzX where X is Br, DH, 1', OH OH CHQXor O CH CHaX I't (I) where R is alkyl or aryl (e.g. phenyl oralkylphenyl) and the average number of phenolic nuclei (units) is 1 to 6per molecule. CRT-328 fits Formula I when R is p-toctyl, the molecularweight is about 500 and the product has about 2831% of Br. 60 to 85% ofthe terminal X units are halogen of atomic weight 80 to 127. Theterminal X units are those which are methylol or halomethyl. By terminalX units is meant those X units which will analyze as methylol orhalomethyl, thus methylene ether bridges analyze as methylol.

Unless otherwise indicated all parts and percentages are by weight.

4 EXAMPLE 1 Highly brominated p-t-butylphenol product Grams (A) 31-134dimethylol p-t-butylphenol condensate 420 (B) Toluene 300 (C) Verseneiron specific 10.5 (D)' 48% aqueous HBr 575 A, B and C were loaded intoa reactor and heated to 50 C., a 20-inch vacuum was applied and D wasadded dropwise over 40 minutes. The product was azeotropically distilledto C. and cooled to room temperature to give a viscous productcontaining 38.8% bromine (85 of the theoretical maximum) and 95.5%solids.

EXAMPLE 2 Preparation of 311-134 condensate Grams (A) p-t-Butyl phenol(10 moles) 1500 (B) 37% aqueous formaldehyde (20.5 moles) 1664 (C) 50%aqueous NaOH 400 (D) 20% aqueous HCl 830 (E) 11 0 1000 (F) H 0 1000 (G)H 0 1000 2 800 A and B were loaded into a 5-liter flask. C was addeddropwise. The heat exotherm was to 42 C. The mixture was held there for2 hours and then allowed to stand overnight. The product was neutralizedto a pH of 4.0 with D and washed 4 times consecutively with E, F, G andH, decanting off the water layer. There was obtained 311- 134 condensatein a yield of 2165 grams, molecular weight 227 (theory 210), percent CHOH of 15.71 (theory 16.2).

EXAMPLE 3 Preparation of CRJ328 (highly brominated p-t-octyl phenolreactive condensate) Grams (-A) Dirnethylol p-t-octylphenol condensatecontaining toluene (258-88) 2480 (B) 48% aqueous 'HBr 1690 A was loadedinto a 5 liter flask and heated to 50 C. Dropwise there was added B over155 minutes. The mixture was held at 50 C. for 1 hour. The mixture wasthen distilled with a 26 inch vacuum to C. and the temperature held for30 minutes, and the product cooled.

Yield of CRP-328 was 1638 grams, 'Br 28.65%, molecular weight 502,viscosity about 15,000 centipoises.

EXAMPLE 4 Preparation of 258-88 condensate A, B and C at 25 C. wereloaded into a flask. D was added at 25-30 C. over '15 minutes. Themixture was held for 48 hours at 25-30 C. and then neutralized with E.The water layer was separated. The residue was washed at 25-30 C. withF, G, H and I, decanting the water layer each time. Then I was added todilute the product.

Yield: 7638 grams (58% solids).

' Gardner-Holdt viscosity: Z -Z 5 EXAMPLE 5 Highly brominated dodecylphenol reactive condensate Grams (A) Dimethylol p-dodecylphenolcondensate (311- 644 (B) Toluene 200 (C) 48% aqueous HBr 575 (D) VerseneIron specific 16.1

A, B and D were loaded into a flask. The mixture was heated to 50' C.and 20 inches of vacuum applied. C was added dropwise over one hour. Themixture was azeotropically distilled with 21 inches of vacuum to 110 C.,held for 10 minutes and cooled to room temperature.

f A and'B were loaded into a reactor and heated to 40 C. Then C wasadded dropwise over 0.5 hour. The mixture was held under 50 C. for twohours and then neutralized with D to pH of 1. The mixture was thenwashed three times consecutively with E, F and G, decanting off thewater layer each time. The product had 71% solids, 9.27% water, 24.95%CH OH and the yield of 311-157 was 3385 grams.

, EXAMPLE 7 Highly iodinated reactive condensate Grams (A) Dimethylolp-t-octylphenol condensate (258-88) 863 (B) FeCl .6H 0.05

(C) 47% aqueous hydroiodic acid 600 A and B were loaded into a flask andheated to 50 C. Then C was added dropwise over 7 minutes. The flask wasset for distillation and distilled to 100 C. at about 21 inches ofvacuum. The mixture was held there for 15 minutes and cooled.

The product had 37.3% I and the yield was 664 grams.

EXAMPLE 8 This example illustrates the formation of a heat reactivehalomethylated condensate which has too little halogen to effect a roomtemperature vulcanization. Hence it is not within the invention.

Grams (A) Dimethylol p-t-octylphenol condensate (258- 88) at 100%-solids -2 200 (B) Versene Iron specific (C) 48% aqueous HBr 104 A and Bwere loaded into a 2 liter flask set up for azeotropic distillation. Themixture was distilled at 26 inches of vacuum to 4550 C. Then C was addedover 5 minutes and the mixture distilled in vacuum to 90 C. and cooled.

Percent Solids 82 Br 20.0

In the subsequent examples the materials used are identified as follows.

Arco CS-l5 is a liquid hydroxyl terminated copolymer of butadiene andstyrene (75:25) having a viscosity of 225 poises at 30 C., hydroxylcontent 0.65 meq./g., equivalent weight of 1538, polybutadienemicrostructure trans-1,4 60%, cis-1,4 20% and vinyl-1,2 20%.

Arco CN-15 is a liquid hydroxyl terminated copolymer of butadiene andacrylonitrile (:15), viscosity of 525 poises at 30 C., hydroxyl content0.60 meq./g. equivalent weight of 1667 and polybutadiene microstructureis the same as for Arco CS-15. The equivalent weight of the Arcoproducts is 1000 OH content Arco R45HT is a liquid hydroxyl terminatedbutadiene homopolymer having a viscosity of 50 poises at 30 C., ahydroxyl content of 0.75 meq./g. and an equivalent Weight of 1250. Thepolybutadiene microstructure is the same as for Arco CS-15.

Arco R15M is a hydroxyl terminated liquid butadiene homopolymer,viscosity 200 poises at 30 C., hydroxyl content 0.70 meq./g., equivalentweight 1428 and polybutadiene microstructure as for Arco CS-15.

Ricon 150 is a sodium polymerized viscous liquid polybutadienecontaining 70% pendent 1,2-vinyl groups, molecular weight approximately2000 (Ricon 100 which can also be used is a viscous liquid sodiumpolymerized butadiene-styrene copolymer (80:20) molecular weight 2000and having 70% pendent 1,2-vinyl groups).

-LM Butyl MD 504 is a viscous liquid isobutyleneisoprene copolymer(about 96:4), molecular weight 30,000 to 35,000. LM chlorobutyl is aviscous liquid chlorinated butyl rubber molecular weight 30,000 to35,000.

Lithene AH is a liquid lithium polymerized phenyl terminatedpolybutadiene, molecular weight 1500-2000, viscosity about 2000 poise at25 C. and has 15% trans 1,4 and 60% vinyl unsaturation and 25%internally cyclized groups.

Lithene PH is a liquid lithium polymerized phenyl terminatedpolybutadiene, molecular weight 2000-3000 viscosity about 66 poises at25 C. and has 10% cis-l,4, 45% trans-1,4 and 45 vinyl unsaturation.

Lithene QH is a liquid lithium polymerized phenyl terminatedpolybutadiene, molecular weight about 3000, viscosity about poises at 25C. and containing 35% cis-1,4, 30% trans-1,4 and 35% vinyl unsaturation.

Hystl C-1000 is a liquid carboxy terminated polybutadiene, molecularweight 1350i150, viscosity 50-200 poises at 45 C., carboxyl content 1.11meg/gram.

Hystl G-1000 is a liquid hydroxyl terminated polybutadiene, molecularweight 13501150, viscosity 25-100 poise at 45 C., hydroxyl content 1.18meq./gram.

Hystl G-2000 is similar to Hystl GF-lOOO but has a molecular weight of2000:200, a viscosity of 100-350 poise at 45 C. and a hydroxyl contentof 0.75 meq./ gram.

Hystl B2000 is a liquid polybutadiene molecular weight 2000:200, havinga viscosity of 30-140 poise at 45 C. and a vinyl content of at least90%.

The new elastomer cure systems containing the highly halomethylatedphenolics are useful in caulks, sealants, adhesives, propellant binders,potting compositions, .encapsulation compounds, in masking tape, e.g. tomake natural rubber have more holding resistance at elevativetemperature by partially vulcanizing the rubber, and in coatings, e.g.to coat a polyurethane foam to protect the foam. This latter'use isparticularly effective when there is employed a hydroxyl terminatedliquid rubber.

As previously stated zinc oxide is preferably present in the compositionbecause its use aids in controlling the pot life of the composition aswell as the ultimate state of cure.

Table I describes the use of various types of zinc oxide as catalystsfor the room temperature vulcanization of Arco RlSM. As one can see, thepot life can be controlled somewhat by using the appropriate zinc oxide.The higher surface area zinc oxides have shorter pot lives.

There were utilized 13 phr. of zinc oxide and 30 phr. of CRJ-328 in thework recorded in Table I.

The term phr. indicates the part per hundred parts of rubber.

- Tables II through VII illustrate the efiect of various levels of ZnOand CRJ-328 on the vulcanization of six liquid elastomers.

It is quite obvious from the tables that zinc oxide has a marked effecton pot life, with increased amounts decreasing pot life significantly.It is also obvious that increased amounts of CRJ-328 cured theelastomers to a higher Shore A hardness.

It has been found that, when utilizing 40 phr. of CRJ 328, the lowerlevels of zinc oxide can initiate an exothermic reaction which isdifiicult to control resulting in the decomposition of the vulcanizate.This decomposition is evidenced by a violent emanation of I-IBr,frothing of the mass and a resultant black, friable product. Higherlevels of zinc oxide prevent these phenomena.

In general, it has been found that CRJ-328 at the 30-part level and zincoxide at the l3-part level gives the best balance of properties andhandling safety for most liquid elastomers. Table VIII presents thestrength properties of a variety of gum liquid elasotmers vulcanizedwith 30 phr. of CRJ-328 and 13 phr. of zinc oxide. Tables IX and Xillustrate the effect of black and white loadings.

ADHESIVE PROPERTIES The tensile shear strength of various substratesbonded with CRJ-328 vulcanized elastomers was also evaluated.

8 After 24 hours aging, attempts to remove the coating from the foamresulted in foam tear, showing the strong adhesion of the cured rubberto the polyurethane foam.

EFFECT OF IMMERSION FOR ONE WEEK AT 25 C. ON CRJ-328 VULCANIZEDELAS'IOMERS CURING OF SOLID ELASTOMERS WITH CRT-328 Formulation: PartsButyl 035 100 HAF black Zinc oxide 5 Stearic acid 1 The aboveformulation was prepared in a Banbury mixer and then transferred to atwo-roll mill where the amounts of CRT-328 indicated in Table XIV wereadded. The stock was then sheeted and pressed for ten minutes at roomtemperature.

Slabs were aged for 24 and 96 hours at 25 C., then physical propertiesmeasured. Results are summarized in Table XIV.

The advantages of the cure system of the invention include a lowtemperature vulcanization and formation of light colored stocks. Thescorchy nature of this cure system is of special value in applicationsrequiring faster cure times at lower temperatures.

TABLE I Efiect of various types of ZnO with CHI-328 in Arco R15M iii ShX surface M dfi 1 e ore area oi at n 1 ZnO type (min.) Color hardness(mJ/g.) ZnO C 0 o Kadox 15 7 Tan 50 10 Kadox 72 11 Tan 52 6 l h. Protox168-. 10 Tan 53 6 Kadox-72 with CHaOHaCOOH; P10tOX169.-- 53 10 Kadox-IBwith 0113011100011; Actox14 3.5 None. Actox 16--. 52 3.6 opao n coo r1'88 e O 8!. Actox 216--- 28 Brown 52 3.5 OHsOHrCiOdH treated 11 t.XX78.--'. 19 Light blOWlL; 3.5 None. pa 6 XX203... 35 .-..do 58 4 Do.Type 601 9 .do 60 2.7 Do.

1 All are products of the New Jersey Zine Company.

The bonded substrates were aged for 72 hours at room temperature beforetesting at two inches per minute sep TABLE 11 aration on a Tinius Olsen.The results are shown in [Am OM15] Table XI.

Fabric peel strength of various substrates utilizing 30 smmAhardmss phr.CRJ-328 and 13 phr. of zinc oxide in Lithene AH PM zno R?- ig M h 96-7days were evaluated and the results are shown in Table X-II. (1533mm328 m? at r liil; The bonded substrates were rolled with a threepound 2oroller then aged for 48 hours at room temperature before 20 .1g 55 2? 3gg? pulling at two inches per minute (T-peel). g8 22 21 36 60 23 Thefollowing formulation was evaluated as a poly- 30 23 i; 2; 38 v 3;urethane foam coating: 30 15 47 55 35 h :2 a a 23 1t ene 49 Zinc oxide 140 1s 66 71 91V 42 3 30 7 1 RT is room temperature.

TABLE III TABLE VI! [Areo R45HT] [Area 0845] Shore A hardness Shore Lhardness Phr. Pot 4am. 96-hr. 1 days 5 Phr. Pot 4am. 9cm! 1 days Phr.ZnO 0111- ll 24-hr. at 158 at 212 water Phr. ZnO CRJ- liie 24-hr. at 158at 212 water (Kadox 15) 328 (min at RT F. F. immersion (Kadox 15) 328(min) at RT F. F. immersion e 11 1a 40 so 15 20 18 as or as as 20 12 2837 25 20 11 24 42 85 20 20 0 15 32 54 14 20 8 24 45 75 27 80 52 52 80 4910 30 13 55 87 82 23 80 6 44 71 93 43 30 7 51 50 70 45 30 5 37 41 70 3130 10 46 51 80 37 40 20 41 73 86 46 40 I10 40 6 58 80 75 61 40 7 0d 7487 d5 40 5 48 82 71 50 40 5 63 70 75 62 Thls formulation enothermed andirothed to a friable black mass TABLE Iv which was unusable. [Rim TABLEvm Shore A hardness [Tensile strength and elongation oi gum elastomersvulcanized at 25 C;

' with 30 parts OBI-328 and 13 parts kadox 15 (zinc oxide)] Phr. Pot48-hr. 96-hr. 7 days Phr. ZnO CRJ- liie 24-hr. at 158 at 212 waterLength Elonga- (Kadox 15) 328 (min.) at RT F. F. immersion 01 time tion,

I at RT, Tensile per- 20 40 20 48 90 22 Elastomer days Shore A (p.s.i.)cent 20 26 16 21 80 15 20 15 20 60 18 LM Butyl MD504 plus 24 80 77 80 492 52 163 80 12 32 38 51 B5 15 85 172 0 30 10 85 38 50 82 14 47 195 10013 13 109 40 l 7 12 57 316 100 40 6 44 59 76 50 2 58 170 40 2 42 100 50I These samples exothermed and irothed to iriable black masses in 17minutes. 1 Flexon 845 is a parafinic hydrocarbon oil of viscosity 150SSU at TABLE v 100 F. (Humble Oil Refining Company.)

30 Norm-The above formulations were pressed in an ASTM mold con-[Lithene AH] forming to Test Method D-us at 75 to 100 p.s.i. for onehour between Teflon sheets ior easy removal. Shore A hardness TABLE IxPot 7 days [Tensile strength and elongation of elastomers loaded withparts FEF Phr. ZnO CBI- llie 24-hr. at 158 at 212 water (Kadox m) 328(min) at RT F. F. immersion 35 black vulcanized at 25 0. with 30 partsC81 328 and 13 parts zinc oxide] Tensile strength 20 84 15 25 45 50 20g: e g g; W 20 F. F. 28 g g g g lwk m: 1Wlr m: 30 m w 60 84 40 Elastomerat RT 70 hrs. at RT 70 hrs. 40 26 i 85 g Lithene AH. see 286 25 1o 40 97 35 g Arco 12.1514 400 42a 30 1a 40 7 72 78 8 Arco cs15 490 not as 20seas n. a; 23% .22 a

11 5 TABLE LM chlorobutyl.... e11 297 as [LM Butyl MD504] 45 iWk=Week.Bhore A hardness P111; 7 days TABLE x Phr. ZnO CBJ- 48-hr. 96-hr. atwater Tensile strength and elongation at elastorners loaded with 60parts (Kakox 15) 328 at 158 F 212 F immersion titanium dioxidevulcanized at 25 C. with 30 parts URI-328 and 13 parts zinc oxide] 27 3024 50 27 20 20 Tensile strength 30 39 26 (p.s.i.) Percent elongation 4040 35 47 46. 40 158 F. 158 F. 39 40 36 1 Wk ior 1 Wk ior 34 1 g; g;Elastomer at RT 70 hrs. at RT 70 hrs. 35 37 32 55 Lithene AH....-.-.-406 785 75 55 415 295 50 30 Norm-Due to the fact that this elastomer isvery viscous, the above 250 315 70 00 formulations were prepared on atwo-roll mill and the pot life could not 870 50 40 be measuredaccurately. The pot life for the above iormulations was 144 188 125 40approximately ten minutes.

TABLE XI (Use 01 URI-828 vulcanized elastomers as adhesives] I Tensileshear (p.s.i.)

Phr. Phr. GRJ- Mylar] Canvas] Plywood Elastomer type ZnO 328 Mylarcanvas plywoo Arco (IS-15...... 2o 20 so a 15 a 30 24 A 30 42 A 40 500191 A 80 53 24 A 30 40 A 1 Indicates substrate failure.

Norm-C =Indicates cohesive failure. A=Indicates adhesive failure.Substrates-Canvas =20-oz. electrical laminating grade cotton duck; GlassCloth= =Type 181 Finish A1100 Hard; Mylar=15 mils. (Mylar is biaxiailyoriented polyethylene terephthalate); Plywood=3 ply interior grade;

Steel=16 gauge, cold rolled.

TABLE XII.FABRIC;T.O FABRIC PEEL STRENGTH H P VX i I 5 Phr.ZnO CRI- 111524-111 415L158 rat-212" water ASTM D-.1S76 2"lmin. test temperature 73F.

{v mi pi un m f ,I V I V (Kadoxlfi) 328 (min-)7 at R'll .F. I F.immersion No'rE.. l' A dhesiyefailure C=Coheslve failure. 7 I I 20 I I i49 NC NC NC v NC Bubstrates.-Mylar=15 mnfoiass Cloth=Type 181, Finish11-1100 20 68 NC 1 NC N NC Herd; Canvas =20-oz. electrical laminatinggrade cotton duck. 20 N NC NC NC 7 NC 1 r 30 24 20 72 92 -42 r 10 30 1924 42 45 4s 30 18 as 40 50 1 2s 40 14 s0- s0 s5 .70 40 12 so so 87'"- Y50 40 30 a5 40- a0 TABLE min-EFFECT or IMMERSION' o1 URI-32s CUREDEnAsToMEns Percent weight gain 7 U V v A I 10% Flexon 4 -A1'co AreoRlcon Llthene Areo 845 Mod Media. cscN-ls- 150 AH R45H'I LM Butyl 4.30.0 5.9 3.0 High Hig'h Hlgh 151 High High High 112 11 18 2:1-

' l The cubes deteriorated badly so that measurement was diflicult. Thecubes were [regmented upon one week submersion. I:

TABLE xIv.- PHYSICAL PROPERTIES OF BU'IYL 035 VULCANIZED WITH (IRE-32's"Aged 24 hours "Aged 96 hours 7 n Percent Percent Amount Tensile elon-Shore A Tensile, elon- Shore 'A. CRT-328 (p.s.i) M105 M300 1 gationhardness (p.s.i.) M100 I Mm I gation hardness 0 Opts 20 as 1,000 43 15051' 90' 955 '45 9.0m--- 70 70 87 1,000 44 412 107 100 050 1 45 12.0pts535 s3 154 935 45 1,300 114 695 520 52 20.0pts 1,240 113 585 445 491,440 285 1,440 s00 52 Modulus. Q g V The use of highly iodomethylatedp-alkylphenol prod- TABLE Xvm 'ucts, e.g. the product of Eiiample 7 inplace of the [Wham PH] CRI-328 also gives cured elastomers. The act1onof the Y iodomethylat'ed compounds, however, is much, more gshmAfaldness rapid anddiflicult to control. The highly bromomethylated ZPhr. Pot 1 48-111; 96-111. 7 days products: of Examples 1 and5jli'kewise can be used 111 figa fg g; y? gig); at ggf; 'place ofCRJ-328 as curing agents.

- Th'e following tables show the curing of addiuonal $2 7 g 8 g; liquidelastomers with (JR-L328. Only more limited curing 20 20 57 20 a5 45 55conditions can be employed to cure these elastomers than g8 2g g2 g3 gg'gg those employed in the previous tables. 50 30 a0 42 52 a5 7 40 e1 4251 95 43 TABLE xv 40 20 45 e2 90 45 mm C4000] 50 40 V 20 4 e1 90- 1 4oShoreAhardness Phr. Pot- 48hr. 96-hr. 7days TAB-LE XIX Phr. ZnO CRJ-life 24 111. at 158 at 212 water [Llthene AL] (K111101151: 328 (mln.)at'RT F immersion Shore A, hardness 20 NC NC NC NC NC 55 22 68 45 Phr.Pot 48-h1. 96-hr. 7 days NC. NC NC NC Phr. 2110 031- life I 24-11:. at158 at 212 water 24; is): 38 3g (Ka'dox 15) 328 (min.) at RT F.immersion 35 N0' NC NO 5.5........... 20 :NC No NC NC NC a5 a4 20 NC NON0 N0 N0 37 100+ 100+ 20 NC NC NC NC N0 27 s0 s3 30 NC NC N0 N0 N0 30 NCNC NC NC NC Norm-NC =no cure. 80 81 N 0 NO N C N C :2, 11 :9 as 11 TABLEXVI 40 15 18 so 90 a5 [Hystl G-IOOO] Nor1s.-NO=N0 cum. 7 Shore Ahardness 65 P111. Pot 7 421m. 90-111. 7days TABLE XX Phi. Z CBJ' life24-h1. at 158 at 212 water [Al-co 315M] (Kadox 15) 328 (min) at RT F.immersion 3g 8 1 g 8 1g1?) 13% 7 Shore A hardness 70 Phr. Pot 48Fhr.96-hr. 7 days g3; Hg NC Q NC P111. ZnO CBJ- lite 2411:. 8115 5: at 212water 2%. M. ufi g" "Lag-r g; 3 (Kadox g (1n ln at RT immersion 5 23 g22 52 is $2 2 :2 40. '4 30 55 85 52 52 Unless otherwise indicated allparts and percentages are by weight. Based on the total of (1) zinccompound, e.g. zinc oxide, and (2) the halomethylated curing agent thezinc compound is usually between 14 and 50% the total of (1) and (2).

What is claimed is:

l. A composition comprising (1) a vulcanizable liquid elastomer which isa polymer of a diolefin, (2) a mixture of alkylated phenol compoundshaving the formula:

where X is CH, halogen of atomic weight 80 to 127,

-O CH CH X where R is alkyl or aryl and the average number of phenolicnuclei is 1 to 6 and 60 to 85% of the terminal X groups are saidhalogen, said mixture of alkylated phenol compounds being present in anamount sufficient to vulcanize said elastomer; a zinc compound selectedfrom the group consisting of zinc oxide, zinc resinate, zinc naphthenateand zinc salicylate in an amount suflicient to control the working lifeof the composition.

2. A composition according to claim 1 wherein the mixture of alkylatedphenols also is a liquid.

3. A composition according to claim 1 wherein said halogen is bromine.

4. A composition according to claim 1 wherein the zinc compound is zincoxide and the halogen is bromine.

5. A composition according to claim 4 wherein the elastomer is a liquidelastomer selected from the group consisting of liquid butadienepolymers and liquid isoprene polymers.

6. A composition according to claim 1 wherein said mixture of compoundsis present in an amount sufiicient to initiate vulcanization at roomtemperature.

7. A composition according to claim 6 including zinc 14 oxide in anamount suflicient to control the working life of the composition.

8. A composition according to claim 7 wherein the liquid elastomer isselected from the group consisting of hydroxy terminated polybutadiene,hydroxy terminated butadiene-styrene copolymer, hydroxy terminatedbutadiene-acrylonitrile copolymer, polyisoprene, polybutadiene andliquid butyl rubber copolymer.

9. A composition according to claim 8 wherein to of the terminal Xgroups are bromine.

10. A composition according to claim 8 wherein R is 8 carbon atom alkyland the bromine is 27 to 32% of the weight of the mixture of compoundsof said formula.

11. A process comprising initiating the vulcanization of the compositionof claim 1 at room temperature.

12. A process according to claim 11 comprising including zinc oxide inthe composition and completing the vulcanization using the exothermicheat of reaction as the sole source of heat.

13. A process according to claim 11 where the halogen is bromine.

14. A process according to claim 13 wherein the composition includeszinc oxide in an amount sufiicient to control the working life of thecomposition.

15. A process according to claim 14 wherein the liquid polymer is liquidpolyisoprene or liquid polybutadiene.

16. A process according to claim 14 wherein the liquid polymer is liquidhydroxy terminated polybutadiene, liquid hydroxy terminatedbutadiene-styrene copolymer, liquid hydroxy terminatedbutadiene-acrylonitrile. I

17. A process according to claim 14 wherein the liquid polymer is liquidisobutylene-isoprene copolymer.

18. A process according to claim 14 wherein R is 8 carbon atom alkyl andthe bromine is 27 to 32% of the weight of the mixture of compounds ofsaid formula.

19. A process according to claim 18 wherein the liquid polymer isselected from the group consisting of liquid polybutadiene, liquidpolyisoprene, liquid butyl rubber, liquid hydroxy terminatedpolybutadiene, liquid hydroxy terminated butadiene-styrene copolymer andliquid hydroxy terminated butadiene-acrylonitrile copolymer.

References Cited UNITED STATES PATENTS 3,489,697 1/ 1970 Brice 260-8463,093,613 6/1963 Fusco et al. 260-846 3,039,978 6/1962 Fusco et al.260-846 3,083,174 3/1963 Fefer et al. 260-846 3,102,104 8/1963 Brice260-846 3,358,051 12/1967 Timmons et a1 260-846 3,165,496 l/l965 Fuscoet al. 260-846 3,096,301 7/1963 Jankowski et al. 260-846 3,028,3534/1962 Elmer et al. 260-846 JOHN C. BLEUTGE, Primary Examiner U.S. Cl.X.R.

260-38, 59, 619 R, 621 K, 623 D, 838, 845, 846, 848

